CN105618078B - A kind of catalyst for ammoxidation alkyl pyridine - Google Patents
A kind of catalyst for ammoxidation alkyl pyridine Download PDFInfo
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- CN105618078B CN105618078B CN201510888905.1A CN201510888905A CN105618078B CN 105618078 B CN105618078 B CN 105618078B CN 201510888905 A CN201510888905 A CN 201510888905A CN 105618078 B CN105618078 B CN 105618078B
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Abstract
The invention discloses a kind of catalyst that cyanopyridine is prepared for ammoxidation alkyl pyridine.It being made of active component and carrier, active component is made of main active material and auxiliary active agent, wherein, main active material is V2O5And Sb2O3, the oxide of auxiliary active agent Fe, Mn, Cr, Co, La, Ce and the salt of Na, Ca or oxide, active component mass content is 1% 35%；Using the alumina balls that titanium is modified as carrier, carrier composition is expressed as by mass content：Al2O3≥90%、TiO2≥3%、SiO2≤0.1%、Fe2O3≤0.04%、Na2O≤0.35%.The catalyst of the present invention prepares cyanopyridine for ammoxidation alkyl pyridine, and reaction temperature is low, catalyst service life is long, the selectivity of product and yield are higher, reduces production cost.
Description
Technical field
The present invention relates to a kind of catalyst, particularly one kind to prepare cyanopyridine for ammoxidation alkyl pyridine
Catalyst, belong to technical field of organic synthesis.
Background technology
In petrochemistry, the reaction of alkyl pyridinium compounds partial oxidation and ammonoxidative nitrile synthesis class be directly related under
Swim the exploitation and production of product such as medicine, pesticide, dyestuff.By taking nicotinonitrile as an example, nicotinonitrile also known as nicotinic acid nitrile are
Niacin and niacinamide can be made in a kind of important medicine intermediate, nicotinic acid nitrile hydrolysis, and niacin and niacinamide are the one of vitamin B
Kind, the extensive application in the industries such as medicine, food and feed additive.3- can be made by Hofmann degradation in niacinamide
Aminopyridine, 3- aminopyridines are used as the intermediate of production treatment gastric ulcer and duodenal ulcer in terms of medicine, in pesticide
Aspect is used as the raw material of fungicide Buthiobate.In recent years, the ammoxidation of 3- picolines prepares nicotinonitrile Catalytic processes
Certain progress is achieved, but there be very big development space in catalyst activity, selectivity and service life.Disclosed in the prior art
Document, Zhejiang Normal University is with rutile titania phase V2O5For main active material, with rutile titania phase TiO2For carrier, reaction temperature control is existed
260-300 DEG C, 3- picolines conversion ratio is 87.1%, and nicotinonitrile is selectively 58.1-94.6%；Wuhan University is with V2O5、
Cr2O3And MoO3For main activating agent, for reaction temperature at 350-400 DEG C, the conversion ratio and nicotinonitrile of 3- picolines are selective
For 90%；Sun Hui etc. is using Vti8Ox as catalytic component main body, and catalyst is catalyzed 3- picolines at 200 DEG C under ebullated bed
Ammoxidation reaction, conversion ratio reaches 99%, and nicotinonitrile yield is more than 98%, but the method operating condition is stringenter,
Control relatively difficult, especially particle collides with each other during exercise, easily smashes, and influences the service life of catalyst.Degussa companies
It is provided in patent US4447612 using the oxide of Sb and V as the catalyst of main active component, but the preparation process of catalyst answers
Miscellaneous, the conversion ratio of alkyl pyridine is relatively low.Mitubshi Gas Chemical companies are in US4963687 with the oxygen of V, Cr, B
The catalyst addition Mo that compound is prepared as main active material is reacted at 390 DEG C as synergistic catalyst, the yield of product with
And the conversion ratio of 3- picolines is relatively low.For this purpose, it is good, long lifespan for ammoxidation to find a kind of high conversion rate, selectivity
Alkyl pyridine prepares the catalyst of cyanopyridine as problem common in the industry.
The content of the invention
The object of the present invention is to provide a kind of catalyst for ammoxidation alkyl pyridine.
The present invention adopts the technical scheme that such：A kind of catalyst for ammoxidation alkyl pyridine, by activearm
Divide and carrier composition, active component are made of main active material and auxiliary active agent, wherein, main active material is V2O5With
Sb2O3, the molar ratio of V and Sb are 1：（0.5-10）, the auxiliary active agent in active component is Fe, Mn, Cr, Co, La, Ce
The oxide of the salt or Na, Ca of oxide and Na, Ca is expressed as in active component, V with molar ratio：Fe：Mn：Cr：Co：La：
Ce：Na：Ca=1:（3-50）:（2-20）:（0. 02-0.5）:（0.002-0.08）:（0.004-0.1）:（0.004-0.2）:
（0.002-0.5）:（0.004-0.1）；Active component mass content is 1%-35%, is preferably 10%-25%；The oxidation being modified with titanium
Aluminium ball is as carrier.
The catalyst of the present invention, the alumina balls appearance and size that carrier titanium is modified are 3-5mm, and carrier composition is by mass content
It is expressed as：Al2O3≥90%、TiO2≥3%、SiO2≤0.1%、Fe2O3≤0.04%、Na2O≤0.35%, the alumina balls that titanium is modified
Bulk density >=200g/m2, specific surface area >=200m2/ g, pore volume >=0.40ml/g, intensity >=60N/.
The preparation method of the catalyst of the present invention is as follows：First by the inorganic salts or oxygen of the oxide and Na, Ca of vanadium and Cr
Compound is dissolved in the aqueous solution of organic acid, is dissolved by heating at 60-80 DEG C, and navy blue solution is made, then molten to this again
Other catalytic components are added in liquid, stirs, obtains the aaerosol solution of active material.Catalyst carrier is placed in the sugar-coat of rotation
In pot, by the suspension spray of active component or it is added drop-wise on dry carrier, until active material reaches estimate, warp
Drying is crossed, up to required catalyst when activation 3-12 is small at 300-500 DEG C.
The catalyst of the present invention prepares cyanopyridine for ammonia oxidation, and the raw material that ammoxidation reaction uses is 2- methyl pyrroles
Pyridine, 3- picolines, 4- picoline one of which.
The catalyst of the present invention prepares cyanopyridine for ammoxidation alkyl pyridine, using method well-known in the art
It carries out, process conditions are：
The ammoxidation reaction of alkyl pyridine carries out in fixed bed reactors, is heat source with the fused salt circulated, bed temperature
With thermocouple measurement, the process conditions of reaction are：
Air speed：1000-2000m3/hr
Alkyl pyridine：100-150g/hr
Ammonia：20-100g/hr
Reaction temperature：280-400℃
In material gas mixture, air is used as oxygen-containing gas, and air can use the inert gas of nitrogen etc to dilute.This is anti-
Should be typically to carry out under normal pressure, the discharge of reactant gas self-retaining bed reactor bottom, and enter absorption through subcooler
Tower obtains solid reaction product.
The method for evaluating catalyst uses following two formula：
What the present invention obtained has the beneficial effect that：Compared with prior art, using the catalyst of the invention prepared and phase
The ammoxidation alkyl pyridine technique answered, reaction temperature is relatively low, and the molar ratio of alkyl pyridine and ammonia is small, the high conversion rate of raw material, production
The high income of object cyanopyridine reduces the production cost of cyanopyridine, has preferable industrial application value.
Specific embodiment
Following embodiment is used to illustrate the present invention.
Embodiment 1
（1）Catalyst preparation
First by 12.73 grams of V2O5And 0.05gCrO3, 0.824g NaCl, 0.40gCaO add in 90g oxalic acid and 800ml together
Deionized water dissolves by heating at 70 DEG C and navy blue aqueous solution is made.103.5g Sb are added in into this aqueous solution2O3、
79.4gFe2O3、1.08gMnO2、0.28g LaCe(CO3)3, 160g formamides stir evenly and active material suspension are made.
The active oxidation aluminium ball 1100g that the titanium of a diameter of 3-5mm is modified is added to the sugar of the rotation of a diameter of 500mm
It in clothing pot, by the suspension spray of active material or is added drop-wise on dry carrier, until catalyst activity content of material is up to 15%
Until.Then 120 drying 12 it is small when, 350 DEG C roasting 10 it is small when, obtain catalyst active materials composition molar ratio be：
V：Sb：Fe：Mn：Cr：Co：La：Ce：Na：Ca=1: 4.8: 6.5: 9.7: 0.08: 0.004: 0.007:
0.007: 0.09: 0.045
（2）Catalyst application
It is 25mm, 1200g catalyst is loaded in the fixed bed reactors of long 3.6m manganese steel in internal diameter, with 3- picoline
For raw material, nicotinonitrile is made in ammoxidation, and process conditions are as follows：
Air speed：1500m3/hr
Alkyl pyridine：120g/hr
Ammonia：23g/hr
310 DEG C of reaction temperature
Reaction result：
3- picoline conversion ratios：99.2%
The yield of nicotinonitrile：99.5%.
Embodiment 2,3
With the identical method for preparing catalyst of embodiment 1 and evaluation method, change catalyst composition and prepare different component
Catalyst, the results listed in the following table：
Embodiment 4,5
Catalyst is prepared with the identical method for preparing catalyst of embodiment 1, changes catalyst application conditions, ammoxidation reaction
Condition is：
Air speed：1800m3/hr
Alkyl pyridine：120g/hr
Ammonia：20g/hr
305 DEG C of reaction temperature
The results listed in the following table：
Claims (2)
1. a kind of catalyst for ammoxidation alkyl pyridine, it is characterised in that it is made of active component and carrier, wherein, activity
Component is made of main active material and auxiliary active agent, and main active material is V2O5And Sb2O3, the molar ratio of V and Sb are 1：
（0.5-10）, the oxide of auxiliary active agent Fe, Mn, Cr, Co, La, Ce and the salt of Na, Ca or oxide, activearm
It is expressed as in point with molar ratio, V：Fe：Mn：Cr：Co：La：Ce：Na：Ca=1:（3-50）:（2-20）:（0. 02-0.5）:
（0.002-0.08）:（0.004-0.1）:（0.004-0.2）:（0.002-0.5）:（0.004-0.1）；Active component mass content
For 1%-35%；Carrier is the alumina balls that titanium is modified.
2. catalyst according to claim 1, it is characterised in that active component mass content is 10%-25%.
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| CN105618078B true CN105618078B (en) | 2018-05-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114950404B (en) * | 2022-05-19 | 2023-11-17 | 中国科学院兰州化学物理研究所 | Wear-resistant ammonia oxidation catalyst and preparation method and application thereof |
| CN115041160A (en) * | 2022-07-20 | 2022-09-13 | 常州新日催化剂股份有限公司 | Fixed bed 2-cyanopyridine catalyst and preparation method and application thereof |
| CN116078371A (en) * | 2022-12-30 | 2023-05-09 | 南通立洋化学有限公司 | Catalyst for preparing 2-cyanopyridine by catalytic ammoxidation and application thereof |
| CN117942976B (en) * | 2024-03-27 | 2024-06-14 | 北京弗莱明科技有限公司 | Ammonia oxidation reaction catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196973A (en) * | 1997-03-27 | 1998-10-28 | 标准石油公司 | Process for preparation of antimonate catalysts for (AMM) oxidation of alkanes and alkenes |
| US6451730B1 (en) * | 1997-06-27 | 2002-09-17 | The Standard Oil Company | Two-stage preparation of promoted V/Sb-oxide ammoxidation catalysts |
| CN1502408A (en) * | 2002-11-27 | 2004-06-09 | 3 | Process for preparing a catalyst for the oxidation and ammonixation of olefins |
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2015
- 2015-12-07 CN CN201510888905.1A patent/CN105618078B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196973A (en) * | 1997-03-27 | 1998-10-28 | 标准石油公司 | Process for preparation of antimonate catalysts for (AMM) oxidation of alkanes and alkenes |
| US6451730B1 (en) * | 1997-06-27 | 2002-09-17 | The Standard Oil Company | Two-stage preparation of promoted V/Sb-oxide ammoxidation catalysts |
| CN1502408A (en) * | 2002-11-27 | 2004-06-09 | 3 | Process for preparing a catalyst for the oxidation and ammonixation of olefins |
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Inventor after: Liu Xiaomin Inventor after: Zhang Weiyan Inventor after: Wu Lang Inventor after: Wang Jialiu Inventor after: Li Duo Inventor after: Li Xinming Inventor after: Zhang Mingcui Inventor after: Shi Hongbo Inventor after: Zhao Liya Inventor after: Zhang Man Inventor after: Li Xueyan Inventor after: Liu Junjuan Inventor after: Wu Xueqiang Inventor after: Li Yanchuan Inventor after: Wang Panqin Inventor after: Liu Zhixin Inventor after: Liang Jianguo Inventor after: Li Shujian Inventor after: Ling Guangxuan Inventor after: Xiang Cong Inventor after: Li Yonghui Inventor after: Wen Ning Inventor before: Liu Xiaomin Inventor before: Zhang Weiyan Inventor before: Wu Lang Inventor before: Wang Jialiu Inventor before: Li Duo Inventor before: Li Xinming Inventor before: Zhang Mingcui Inventor before: Shi Hongbo Inventor before: Zhao Liya Inventor before: Zhang Man Inventor before: Li Xueyan Inventor before: Liu Junjuan Inventor before: Wu Xueqiang Inventor before: Li Yanchuan Inventor before: Wang Panqin Inventor before: Liu Zhixin Inventor before: Liang Jianguo Inventor before: Li Shujian Inventor before: Ling Guangxuan Inventor before: Xiang Cong Inventor before: Li Yonghui Inventor before: Wen Ning |
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